Carboxamide substituted tetramethylcyclopentadiene – synthesis, characterisation and its iridium( iii ) complex catalysed reduction of imines. Mwansa, J. M., Stirling, M. J., Sweeney, G., Hanusek, J., Váňa, J., & Page, M. I. Dalton Transactions, 2022. doi abstract bibtex The novel dimeric iodo-iridium( iii ) complex bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised, characterised and its catalytic activity has been evaluated in the transfer hydrogenation of imines. The novel dimeric iodo-iridium( iii ) complex, [Ir(Cp*CONMe 2 )I 2 ] 2 , (Cp*CONMe 2 = η 5 - N,N -2,3,4,5-hexamethylcyclopenta-2,4-diene carboxamide) bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised and characterised. The ligand Cp*CONMe 2 is synthesised as two regioisomers, however the 2-substituted isomer exists as two distinguishable conformers due to restricted rotation about the amide carbonyl carbon and the ring carbon. The relative acidities of Cp*CONMe 2 and Cp* are compared by their relative rates of H/D exchange. The iridium complex of N,N -2,3,4,5-hexamethylcyclopenta-2-4-diene carboxamide [IrCp*CONMe 2 ] and ( R,R )-1,2-diphenyl- N ′-tosylethane-1,2-diamine (( R , R )-TsDPEN) has been evaluated in the transfer hydrogenation of imines under acidic conditions – a 5 : 2 molar ratio of formic acid : triethylamine as the hydride source for the transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline (DHIQ) and its 6,7-dimethoxy derivative in acetonitrile. A decreasing enantiomeric excess with reaction progress is attributed to different kinetic orders for formation of the two product amine enantiomers. The pseudo zero-order formation of the R -amine may be due to a pre-steady-state formation of the less stable form of the diastereomeric catalyst. By contrast, both enantiomeric amines from 1-fluorinated methyl DHIQs as substrates for reduction are formed by pseudo first-order processes.
@article{mwansa_carboxamide_2022,
title = {Carboxamide substituted tetramethylcyclopentadiene – synthesis, characterisation and its iridium( iii ) complex catalysed reduction of imines},
issn = {1477-9226},
doi = {10.1039/d2dt00149g},
abstract = {The novel dimeric iodo-iridium( iii ) complex bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised, characterised and its catalytic activity has been evaluated in the transfer hydrogenation of imines. The novel dimeric iodo-iridium( iii ) complex, [Ir(Cp*CONMe 2 )I 2 ] 2 , (Cp*CONMe 2 = η 5 - N,N -2,3,4,5-hexamethylcyclopenta-2,4-diene carboxamide) bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised and characterised. The ligand Cp*CONMe 2 is synthesised as two regioisomers, however the 2-substituted isomer exists as two distinguishable conformers due to restricted rotation about the amide carbonyl carbon and the ring carbon. The relative acidities of Cp*CONMe 2 and Cp* are compared by their relative rates of H/D exchange. The iridium complex of N,N -2,3,4,5-hexamethylcyclopenta-2-4-diene carboxamide [IrCp*CONMe 2 ] and ( R,R )-1,2-diphenyl- N ′-tosylethane-1,2-diamine (( R , R )-TsDPEN) has been evaluated in the transfer hydrogenation of imines under acidic conditions – a 5 : 2 molar ratio of formic acid : triethylamine as the hydride source for the transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline (DHIQ) and its 6,7-dimethoxy derivative in acetonitrile. A decreasing enantiomeric excess with reaction progress is attributed to different kinetic orders for formation of the two product amine enantiomers. The pseudo zero-order formation of the R -amine may be due to a pre-steady-state formation of the less stable form of the diastereomeric catalyst. By contrast, both enantiomeric amines from 1-fluorinated methyl DHIQs as substrates for reduction are formed by pseudo first-order processes.},
journal = {Dalton Transactions},
author = {Mwansa, Joseph M. and Stirling, Matthew J. and Sweeney, Gemma and Hanusek, Jiří and Váňa, Jiří and Page, Michael I.},
year = {2022},
}
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The novel dimeric iodo-iridium( iii ) complex, [Ir(Cp*CONMe 2 )I 2 ] 2 , (Cp*CONMe 2 = η 5 - N,N -2,3,4,5-hexamethylcyclopenta-2,4-diene carboxamide) bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised and characterised. The ligand Cp*CONMe 2 is synthesised as two regioisomers, however the 2-substituted isomer exists as two distinguishable conformers due to restricted rotation about the amide carbonyl carbon and the ring carbon. The relative acidities of Cp*CONMe 2 and Cp* are compared by their relative rates of H/D exchange. The iridium complex of N,N -2,3,4,5-hexamethylcyclopenta-2-4-diene carboxamide [IrCp*CONMe 2 ] and ( R,R )-1,2-diphenyl- N ′-tosylethane-1,2-diamine (( R , R )-TsDPEN) has been evaluated in the transfer hydrogenation of imines under acidic conditions – a 5 : 2 molar ratio of formic acid : triethylamine as the hydride source for the transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline (DHIQ) and its 6,7-dimethoxy derivative in acetonitrile. A decreasing enantiomeric excess with reaction progress is attributed to different kinetic orders for formation of the two product amine enantiomers. The pseudo zero-order formation of the R -amine may be due to a pre-steady-state formation of the less stable form of the diastereomeric catalyst. By contrast, both enantiomeric amines from 1-fluorinated methyl DHIQs as substrates for reduction are formed by pseudo first-order processes.","journal":"Dalton Transactions","author":[{"propositions":[],"lastnames":["Mwansa"],"firstnames":["Joseph","M."],"suffixes":[]},{"propositions":[],"lastnames":["Stirling"],"firstnames":["Matthew","J."],"suffixes":[]},{"propositions":[],"lastnames":["Sweeney"],"firstnames":["Gemma"],"suffixes":[]},{"propositions":[],"lastnames":["Hanusek"],"firstnames":["Jiří"],"suffixes":[]},{"propositions":[],"lastnames":["Váňa"],"firstnames":["Jiří"],"suffixes":[]},{"propositions":[],"lastnames":["Page"],"firstnames":["Michael","I."],"suffixes":[]}],"year":"2022","bibtex":"@article{mwansa_carboxamide_2022,\n\ttitle = {Carboxamide substituted tetramethylcyclopentadiene – synthesis, characterisation and its iridium( iii ) complex catalysed reduction of imines},\n\tissn = {1477-9226},\n\tdoi = {10.1039/d2dt00149g},\n\tabstract = {The novel dimeric iodo-iridium( iii ) complex bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised, characterised and its catalytic activity has been evaluated in the transfer hydrogenation of imines. The novel dimeric iodo-iridium( iii ) complex, [Ir(Cp*CONMe 2 )I 2 ] 2 , (Cp*CONMe 2 = η 5 - N,N -2,3,4,5-hexamethylcyclopenta-2,4-diene carboxamide) bearing an amide moiety within the tetramethylcyclopentadiene ring, has been synthesised and characterised. The ligand Cp*CONMe 2 is synthesised as two regioisomers, however the 2-substituted isomer exists as two distinguishable conformers due to restricted rotation about the amide carbonyl carbon and the ring carbon. The relative acidities of Cp*CONMe 2 and Cp* are compared by their relative rates of H/D exchange. The iridium complex of N,N -2,3,4,5-hexamethylcyclopenta-2-4-diene carboxamide [IrCp*CONMe 2 ] and ( R,R )-1,2-diphenyl- N ′-tosylethane-1,2-diamine (( R , R )-TsDPEN) has been evaluated in the transfer hydrogenation of imines under acidic conditions – a 5 : 2 molar ratio of formic acid : triethylamine as the hydride source for the transfer hydrogenation of 1-methyl-3,4-dihydroisoquinoline (DHIQ) and its 6,7-dimethoxy derivative in acetonitrile. A decreasing enantiomeric excess with reaction progress is attributed to different kinetic orders for formation of the two product amine enantiomers. The pseudo zero-order formation of the R -amine may be due to a pre-steady-state formation of the less stable form of the diastereomeric catalyst. By contrast, both enantiomeric amines from 1-fluorinated methyl DHIQs as substrates for reduction are formed by pseudo first-order processes.},\n\tjournal = {Dalton Transactions},\n\tauthor = {Mwansa, Joseph M. and Stirling, Matthew J. and Sweeney, Gemma and Hanusek, Jiří and Váňa, Jiří and Page, Michael I.},\n\tyear = {2022},\n}\n\n\n\n","author_short":["Mwansa, J. M.","Stirling, M. J.","Sweeney, G.","Hanusek, J.","Váňa, J.","Page, M. I."],"key":"mwansa_carboxamide_2022-1","id":"mwansa_carboxamide_2022-1","bibbaseid":"mwansa-stirling-sweeney-hanusek-va-page-carboxamidesubstitutedtetramethylcyclopentadienesynthesischaracterisationanditsiridiumiiicomplexcatalysedreductionofimines-2022","role":"author","urls":{},"metadata":{"authorlinks":{}},"html":""},"bibtype":"article","biburl":"https://bibbase.org/zotero/FRGBergamini","dataSources":["o2mL7kG99iAQPpNRJ"],"keywords":[],"search_terms":["carboxamide","substituted","tetramethylcyclopentadiene","synthesis","characterisation","iridium","iii","complex","catalysed","reduction","imines","mwansa","stirling","sweeney","hanusek","váňa","page"],"title":"Carboxamide substituted tetramethylcyclopentadiene – synthesis, characterisation and its iridium( iii ) complex catalysed reduction of imines","year":2022}